Refining hydrocarbon oils



Patented Aug. 21, 1928. a

\ UNITED STATES v 1,681,638 PATENT OFFICE.

EIRAM J. HALLE, OF NEW YORK, N. Y., ASSIGNOR TO UNIVERSAL OIL PRODUCTSGOI- PANY, OF CHICAGO, ILLINOIS, A. CORPORATION OF SOUTH DAKOTA.

. anrmme HYDROCARBON one.

No Drawing. Application filed llay 12, 1920, Serial No. 380,762.,Renewed February 12, 1927.

My invention relates toa process of refining hydrocarbon oils for'theproduction of marketable gasoline and hydrocarbon sulfonic acids.

Among the salient objects of my invention are to provide a process forthe production of water white gasoline or light oils; to provide aprocess for the production of sulfonic acids of the series ofhydrocarbons in cracked oils, straight run oils from crude petroleum andthermal decomposition of coal oil shales and lignites.

The process consists essentiall of distilling the hydrocarbon oil througa column of hot sulfuric acid of varying strengths (depending upon thetype of hydrocarbon oil to be treated) while the hydrocarbon material isin vapor form.

A typical method of o erationis to charge the still with the h rocarbonoil to be treated, the vapor out et of the still passing to the bottomof the column of sulfuric acid which is maintained at a slightly highertemperature at times than the vapor coming off the still. The sulfuricacid reacts with part of the hydrocarbon forming sulfonic acids oflatter, while the oil vapors pass on through water and caustic soda forneutralization, ielding marketable gasoline.

A typicai hydrocarbon oil such as a California cracked oil willillustrate my process, as to products, yields and losses.

. I have successfully treated California oil in the manner hereinbeforementioned with sulphuric acid with concentrations of 20, 55,. 70, and95%. With a concentration 0 20% a charge-of 400 cc. was distilled and.yielded a gasoline percent of 52.1 of a Baum gravity of 61.1. A similarquantity of oil when distilled with a 40% solution ofsulphuric acidyielded 51.2 gasoline with a' Baum gravity of 61.8 with a 55% solution agasoline yield of approximately 50% was obtainable of a Baum gravity of60.6.

p Greater quantities of sulphuric acid did not produce such high ieldsof gasoline and for instance, we foun that with a 70% solution agasoline percentage of 41.0 could be obtained with a gravity of 64.5.

The sulfuric acid sludges varied in color from light reddish to deepblack as'a function of the concentration'of the acid used.

The. ercentage and type of sulfonic acids varie also as a function ofthe acid concentration. The concentrated sulfuric acid roduced a deepblack tar which upon coolmg was highly viscous and asphaltic incharacter showing a highly polymerizing effect upon the hydrocarbons,producing sulfonic acids of high. molecular weight whereas the lessconcentrated acid produced relatively simple molecular weight sulfonicacids of part of the hydrocarbons of the starting hydrocarbons.

Another set of tests were carried out using hydrochloric acid instead ofsulfuric acid, in a similar manner. The products formed were water whitegasoline from the reaction (after neutralizing the oil layer) andchlorides of hydrocarbons in the hydrochloric acid sludge which was of acherry red color at the end of the tests, depending upon theconcentration of acid used. The Water from the acid distilling over withthe hydrocarbon vapors from the acid converter was of y a yellow toorange color. The chloridesas well as the sulfonic acids hydrocarbonscan be readily converted into alcohols and'acetates by well knownorganic reaction. I

I claim as my invention: Y

1. A refining process consisting in passing oil vapors through a columnof heated sulphuric acid maintained at a temperature at least equal tothe temperature of the oil vapors, said acid being in excess ofconcentration of 20% and not exceeding 55%, and in subjecting the vaporsof said acid treatment to a neutralizing treatment to produce gasoline.1

2. A process for refining hydrocarbons which comprises introducinghydrocarbon oil to a still, in subjecting oil in the still to atemperature sufiicient to vaporize substantial portions thereof, andpassing vapors thus formed through a column of sulphuric acid in excessof concentration of 20% and not exceeding 55% and in subjecting thevapors of said acid treatment. to a neutralizing treatment to producegasoline.

3. The step in a process for refining hydrocarbons which comprisespassing the hydrocarbons being treated while in vaporous form through asulphuric acid solution in excess of concentration of 20% and not 106exceeding 55%.

HIRAM J. HALLE.

